WO2004096876A1

WO2004096876A1 - Method for producing polyorganosiloxane-containing resin

Info

Publication number: WO2004096876A1
Application number: PCT/JP2004/005345
Authority: WO
Inventors: Kazunori Saegusa; Tomoyuki Yoshimi; Hiroshi Tone
Original assignee: Kaneka Corporation
Priority date: 2003-04-28
Filing date: 2004-04-14
Publication date: 2004-11-11
Also published as: EP1619213A1; US7393915B2; AU2004234224A1; TW200500418A; CA2522464A1; JP4763458B2; AU2004234224A2; US20060258821A1; JPWO2004096876A1; KR20060007026A; EP1619213A4; CN1777625A

Abstract

A novel method for producing a polyorganosiloxane-containing resin accompanied by reduction of a volatile siloxane is disclosed. The method for producing a polyorganosiloxane-containing resin is characterized by heat-stripping of a polyorganosiloxane-containing resin which is in the form of slurry.

Description

Description Method for producing polyorganosiloxane-containing resin

The present invention relates to a method for producing a polyorganosiloxane-containing resin, a polyorganosiloxane-containing resin obtained by the method, and a flame retardant containing the polyorganosiloxane-containing resin. Further, the present invention relates to a method for separating volatile siloxanes distilled off in the method for producing a polyorganosiloxane. Background art

Polyorganosiloxane or polyorganosiloxane-containing resin improves impact resistance by utilizing physical properties based on the excellent low-temperature properties of the polyorganosiloxane component and its unique reaction, etc. · Used for various purposes such as coating.

Furthermore, from the viewpoints of environmental considerations and safety, and from the viewpoint of handleability represented by viscosity and heat transfer efficiency, it is necessary to be able to manufacture, store, and handle polyorganosixane-xan-containing resins dispersed in aqueous media. The demands are large and form a large market. As a method of producing an emulsion in which a polyorganosiloxane is finely dispersed in an aqueous medium, a method of emulsion-polymerizing a cyclic siloxane or an alkoxysilane under acidic or basic conditions is generally known (US Patent No. No. 289 1920 Specification). Since this reaction is an equilibrium reaction between polycondensation forming a siloxane bond (Si-o-si) from silanol (Si-OH) and depolymerization by hydrolysis, the polymerization is terminated particularly in the presence of an aqueous medium. That is, when the equilibrium is reached, a low molecular weight volatile siloxane is generated. This volatile siloxane does not decrease remarkably even when the polymerization of the bullet-based monomer is further performed. Therefore, the volatile siloxane is isolated from the emulsion or the like by coagulation, dehydration, and drying of the polyorganosiloxane or a resin containing the same, or by spray drying, or applied, When the aqueous medium is removed by coating, etc., it is not only wasted as a raw material but also adversely affects the performance of the coating film, etc. because it is dissipated into the atmosphere together with the aqueous medium as exhaust gas. was there. Therefore, much research has been conducted to obtain emulsions with reduced volatile siloxanes.

(Modification) Using silicone oil or a siloxane oligomer as a starting material, solvent extraction (Japanese Patent Application Laid-Open No. 07-330905) or heating under reduced pressure (Japanese Patent Application Laid-Open No. 07-278473), After removing low-molecular-weight siloxanes by extraction with supercritical or supercritical carbon dioxide (Japanese Patent Application Laid-Open No. 06-107796), they are finely dispersed in an aqueous medium by mechanical means under high-pressure shear. It is easily conceivable to manufacture emulsions. Further, a method of stopping the polymerization / depolymerization reaction by further neutralizing it after further condensation reaction is also known (Japanese Patent Application Laid-Open No. 2001-288826, Japanese Patent Application Laid-Open No. 2 2 2 5 5 4). The emulsion of polyorganosiloxane obtained by these methods contains only a small amount of low molecular weight volatile siloxane, but the stability of the emulsion is poor, and problems such as separation of the polyorganosiloxane and the aqueous medium occur when stored for a long time. You have to.

In addition, the obtained emulsion had a wide particle size distribution, and there was a problem that the subsequent graft modification reaction in producing a polyorganosiloxane-containing resin could not be carried out uniformly.

A method for obtaining a polyorganosiloxane emulsion that does not impair the stability and does not involve the separation of the polyorganosiloxane even during long-term storage, that is, a nonionic surfactant 'ionic surfactant' emulsifies cyclic organosiloxane in the presence of a polymerization catalyst An example is shown in which the volatile siloxane is reduced in the method of polymerization (European Patent No. 45950). However, not all volatile siloxanes are reduced. Further, a similar example is shown in a method in which a polyfunctional silane having three or more functional groups is used in combination while controlling the gel fraction (US Pat. No. 5,661,215). This is presumed to be due to the fact that the probability of generating volatile siloxanes was reduced by introducing a crosslinked structure into the siloxane skeleton.However, although the gel fraction of the resulting polyorganosiloxane was controlled, the ultimately obtained polyorganosiloxane was obtained. Organoshiroki In some cases, a molded article obtained from the sun-containing resin or its composition became brittle and could not exhibit sufficient mechanical strength.

As another method of obtaining an emulsion with reduced volatile siloxane, a method of performing heat stripping is disclosed (US Pat. No. 4,604,336). However, in this method by the batch method, the volatile siloxane is reduced, but the viscosity of the polymer in the emulsion, that is, the molecular weight is reduced.

-As shown in No. 249582.

The invention described in Japanese Patent Application Laid-Open No. 2002-248952 provides a means for simultaneously solving the problem of molecular weight reduction, in which a polyorganosiloxane emulsion is supplied to a continuous flowing device through a stripping gas. This is a technology that allows heating and stripping to be completed in a short period of time by continuously circulating it. However, this method requires a dedicated device for continuous stripping.

Japanese Patent Application Laid-Open No. 2002-284847 discloses a method for solving the problem of a decrease in the molecular weight of polyorganosiloxane without using a dedicated device for continuous stripping and using a batch method for stripping. In this technique, low molecular weight siloxanes such as cyclic siloxanes are subjected to suspension polymerization in the presence of a polymerization catalyst to obtain an emulsion, and after neutralizing the polymerization catalyst, the amount of volatile siloxanes is reduced by batch stripping, and the polymerization is repeated. It shows a method of restarting the condensation reaction by adding a cocatalyst and further neutralizing the mixture. In this method, the operation of adding and neutralizing the polymerization catalyst is repeated, so that the operation becomes complicated, and improvement is desired from the viewpoint of productivity.

As another method, there has been disclosed a method in which kieselguhr is added to a polyorganosiloxane latex, and the mixture is stirred to adsorb low molecular weight siloxane, followed by filtration and removal (US Pat. No. 5,922,022). No. 108). In this method, it was necessary to secure a method for treating kieselguhr adsorbing low-molecular-weight siloxane.

All of the above-mentioned conventional technologies have an effect of reducing volatile low-molecular-weight siloxane, but it is necessary to treat the polyorganosiloxane or the resin containing the same in the form of an emulsion. No method is disclosed for reducing volatile siloxanes in slurry form. For example, a fluid containing volatile siloxanes and hydrocarbons, such as pentane, such as exhaust gas generated during the production of polyorganosiloxane-containing resins, is passed through a column filled with kieselguhr (Foi 1) to form volatile siloxanes and hydrocarbons. U.S. Patent discloses a method in which only hydrocarbons are desorbed by dry air, and then volatile siloxanes are desorbed and recovered by steam and water, and the kieselguhr in the column is further dried and recycled. No. 5,922,108. This method is superior in that it can separate hydrocarbons and volatile siloxanes. On the other hand, dedicated equipment is required, and there is a problem in that the equipment becomes larger for industrial use. Finally, a separate equipment for separating volatile siloxane and an aqueous medium is required. For emulsion systems that do not use hydrocarbons as solvents, etc., which are to be handled by the present invention, simpler methods are desired. Disclosure of the invention

An object of the present invention is to provide a novel method for producing a polyorganosiloxane-containing resin in which volatile low-molecular-weight siloxane is reduced, and a polyorganosiloxane-containing resin obtained by the production method and the polyorganosiloxane. An object of the present invention is to provide a flame retardant containing a contained resin. Still another object of the present invention is to provide a method for separating and recovering volatile siloxane distilled off in the method for producing a polyorganosiloxane-containing resin.

The present inventors have made intensive studies on the above problems, and as a result, have found that volatile siloxane can be reduced by heating and stripping a polyorganosiloxane-containing resin slurry, and have completed the present invention.

That is, the present invention

(1) A method for producing a polyorganosiloxane-containing resin, which comprises reducing volatile siloxane by heating and stripping a slurry of the polyorganosiloxane-containing resin. (2) The method for producing a polyorganosiloxane-containing resin as described above, wherein the slurry-like polyorganosiloxane-containing resin is obtained by coagulating a latex-state polyorganosiloxane-containing resin.

(3) A polyorganosiloxane-based resin obtained by polymerizing a monofunctional and / or polyfunctional radical polymerizable monomer in one or more stages in the presence of polyorganosiloxane-based particles. The method for producing a polyorganosiloxane-containing resin according to the above, which is a coalesced resin.

(4) The method for producing a polyorganosiloxane-containing resin according to any one of the above, wherein the resin is heated and stripped at 100 ° C or higher.

(5) The method for producing a polyorganosiloxane-containing resin according to any one of the above, wherein the slurry is supplied with steam.

(6) The method for producing a polyorganosiloxane-containing resin composition according to any one of the above, wherein the volatile siloxane is separated by cooling a distillate component containing the volatile siloxane.

(7) The method for producing a polyorganosiloxane-containing resin according to the above, wherein the volatile siloxane is separated by cooling a distillate component containing the volatile siloxane to 17 ° C. or lower.

(8) The method for producing a polyorganosiloxane-containing resin described above, wherein the volatile siloxane is separated as a solid when the volatile siloxane is separated.

(9) A polyorganosiloxane-containing resin having reduced volatile siloxane produced by the method described above.

(10) A flame retardant containing the polyorganosiloxane-containing resin described above.

(11) A resin composition comprising the polyorganosiloxane-containing resin described above and one or more resins selected from a thermoplastic resin, a thermosetting resin, and an elastomer.

The present invention is characterized in that volatile siloxane is reduced by heating and stripping a slurry-like polyorganosiloxane-containing resin. The slurry-like polyorganosiloxane-containing resin or the resin composition used in the present invention is obtained by, for example, salting out a latex-like polyorganosiloxane-containing resin or the like with a salt such as chloride, magnesium chloride, or aluminum chloride, or It is preferably obtained by coagulation by a method of treating with an acid such as hydrochloric acid. At that time, it can be coagulated with a latex of another resin, for example, a polymethyl methacrylate resin, a poly (meth) acrylate resin, a polystyrene resin, or a slurry. Note that latex here is a concept that includes emulsion.

The heating stripping may involve foaming from the slurry liquid level, and an antifoaming agent or the like can be added as needed for the purpose of preventing the foaming. The slurry itself has a relatively large particle diameter with respect to the film thickness of the foam, so that the surface tension of the foam tends to be uneven, and the effect of suppressing the formation of foam is large. In particular, the slurry obtained by coagulating a latex-like polyorganosiloxane-containing resin significantly reduces the activity of the surfactant present in the latex during coagulation, and foams more than when stripping from emulsion. In some cases, it is possible to use a small amount or even no use of an antifoaming agent even when using an antifoaming agent.However, when using an antifoaming agent, the type and amount of the antifoaming agent are not limited. And an emulsion defoamer composition containing silica, silicone oil and a surfactant, and a block copolymer of ethylene oxide and propylene oxide. In addition, a method of defoaming by steam contact or cooling using equipment such as a foam separator device can also be adopted.

The weight average particle size of the slurry is not limited, but is preferably at least 1 μm, more preferably at least 10 ^ um, particularly preferably at least 5 μππι, and the upper limit is particularly limited. There is no. If it is less than 1 μπι, the resin is dispersed in a colloidal state, so that it may be difficult to separate the resin from the aqueous medium later, or it may be easy to foam. Further, the shape of the slurry is not limited, and may be not limited to a spherical shape but may be an irregular shape. However, when a slurry is formed by aggregation of emulsion, the slurry shape is often irregular. In addition, In the present invention, the weight average particle diameter can be substituted by the volume average particle diameter.

The polyorganosiloxane-containing resin in the present invention is not limited, but when incorporated into a thermoplastic resin, a thermosetting resin, an elastomer, etc., it is well dispersed in a matrix, and has impact resistance, and in some cases, flame retardancy. From the viewpoint that the above-mentioned functionality can be imparted, the polyorganosiloxane-containing resin is preferably a graft copolymer obtained by grafting a component for dispersing satisfactorily in the resin.

Examples of the polyorganosiloxane-containing graft copolymer include 1,3,5,7-octamethylcyclotetrasiloxane (D4) as disclosed in JP-A-2000-226420 and JP-A-2000-834392. ), Such as cyclic siloxanes, dimethyldimethoxysilane, tetrapropyloxysilane (TPOS), and bifunctional or more alkoxysilanes, and 3_metharyloyloxypropyldimethoxymethylsilane and 3-mercaptopropyldimethoxymethylsilane. Aqueous media such as graphitic crosslinkers, surfactants such as sodium dodecylbenzenesulfonate (SDBS), organic acids such as dodecylbenzenesulfonate (DBSA), inorganic acids such as sulfuric acid and hydrochloric acid, sodium hydroxide, etc. Preferably a latex-like polyorganopolymer obtained by polymerization in the presence of a polymerization catalyst such as a base In the presence of siloxane particles, (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate; aromatic vinyl aldehyde compounds such as styrene; vinyl cyanide compounds such as atarilonitrile; (Meth) acrylic acid such as (meth) acrylamide

Obtained by one or more polymerizations of monofunctional (alkyl) amides and other radically polymerizable monomers such as zyl or aryl (meth) acrylates, allylic esters such as diaryl phthalate, and polyfunctional monomers such as benzene. .

The emulsion particles of the polyorganosiloxane-containing graft polymer preferably have a weight average particle diameter of at least 0.3 μπι, more preferably at least 0.03 izm, particularly preferably at least 0.05 // m, preferably at least 20. μm or less, more preferably 2 // m or less, particularly preferably 0.8 / xm or less. 0.Production of less than μ るもの μπι may be difficult to produce, and those of more than 20 μπι may result in poor storage stability. There is fear. For the purpose of narrowing the particle size distribution of the polyorganosiloxane-based particles, butyl (meth) atalylate distyrene was used at the time of polymerization of a cyclic siloxane, an alkoxysilane, or the like. Latex composed of seed particles having a weight average molecular weight (Mw) of preferably 0.6 m or less or preferably 100,000 or less can be used.

Further, before polymerizing the monofunctional and / or polyfunctional radical polymerizable monomer, an inorganic metal salt such as sodium sulfate is added to the latex containing the polyorganosiloxane-based particles to form a latex particle. Can also be enlarged.

Surfactant · When a polymerization catalyst such as dodecylbenzene sulfonic acid or its sodium salt that cannot be coagulated by acid treatment is used, a method of salting out can be employed as described above.

In the method of the present invention, when stripping the polyorganosiloxane-containing resin slurry by heating, either a batch method or a continuous method may be employed. In the case of the batch method, the slurry is introduced into a pressure-resistant batch distillation apparatus as required before performing the stripping treatment, or a latex-like polyorganosiloxane-containing resin emulsion is introduced into the batch distillation apparatus. After salting out, it is solidified. Thereafter, the temperature of the internal slurry is increased by heating, preferably at least 100 ° C, more preferably at least 120 ° C, further at least 140 ° C, preferably at most 180 ° C, more preferably Is maintained at a temperature of 160 ° C or less, and further, a temperature of 150 ° C or less. The higher the processing temperature, the more effectively the volatile siloxane can be reduced in a shorter time. However, if the temperature exceeds 180 ° C, decomposition of polyorganosiloxane may occur. When the treatment temperature is lower than 100 ° C., the time until the volatile siloxane is sufficiently reduced may be long, or the volatile siloxane may not be sufficiently reduced.

Heating and raising the temperature of the internal slurry can be achieved by heating from the outer jacket of the equipment, heating with a closed steam coil installed in the equipment, introducing steam directly into the slurry, or a combination of these. It can be carried out. When steam is introduced, a higher vaporization efficiency of volatile siloxane is obtained, which is preferable. It is also preferred that the feed be provided through a number of small holes, using a well-arranged perforated vapor spray, and that the feed be provided at a considerable depth from the internal slurry level, preferably from the bottom of the batch distillation apparatus. preferable.

While maintaining the temperature, the volatile siloxane is discharged from the upper part of the batch distillation apparatus together with water vapor as a distillate. At this time, the supplied liquid amount and the discharged liquid amount do not need to be completely equal, but it is preferable to adjust the water amount so as not to remove excessive water. To adjust the water content, it is possible to introduce new water directly into the batch distillation apparatus, and it is also possible to return the water recovered from the distillate components by the method described below into the batch distillation apparatus. However, a method based on steam supply is preferably used because both functions of heating and water supply can be achieved simultaneously. The time for keeping the above temperature and discharging the distillate from the upper part of the batch distillation apparatus (treatment time) is not particularly limited, but is preferably 4 hours or less, more preferably 2 hours or less, depending on the treatment temperature. Is 1 hour or less, more preferably 45 minutes or less, preferably 10 minutes or more, and more preferably 20 minutes or more. If the treatment time is too short, the volatile siloxane is not sufficiently reduced, and if the treatment time is too long, the productivity is reduced and the decomposition of the polyorganosiloxane may occur, which is not preferable.

When the slurry is allowed to stand, the resin component may settle. In this case, not only does the stripping efficiency decrease, but also problems such as the sedimented resin fusing and coarsening, and fusing to the inner wall of the distillation apparatus may be caused. In order to prevent this, slurry is introduced into the batch distillation apparatus, or the latex-like polyorganosiloxane-containing resin is introduced and solidified. It is preferable to continue stirring until discharging.

The slurry remaining in the batch distillation apparatus after the stripping treatment is made of a polyorganosiloxane-containing xane-containing resin having a reduced content of volatile siloxane. The polyorganosiloxane-containing resin can be recovered as a powder or crumb by dehydrating and drying it if necessary. When the heating stripping is performed by a continuous method, the polyorganosiloxane-containing resin which has been previously slurried is passed through a continuous flow device. The continuous flow device may be in the form of a tube, a tube, a tank, or the like. In the case of using a tube, various shapes such as a straight tube, a circular tube, and a spiral tube may be used. In the case of using a straight tube or a tube, it can be circulated in, for example, a vertical descending direction, a vertical rising direction, a horizontal direction, or the like. From the viewpoint of preventing blockage by the resin, a straight tube, a tube, or a tank is preferable, and a straight tube or a tube is preferably used to reduce uneven processing time between individual slurry particles. . When steam is supplied for the same reason as in the batch method, a vertical straight tube, tube, or tank is preferably used.

In the case of the continuous method, the temperature conditions and time for stripping are the same as in the batch method, and the required processing time and continuous flow equipment of an appropriate size are adopted according to the amount of slurry processed. . The same conditions as in the batch method can be applied to the heating method.

Even in the continuous process, the distillate component containing volatile siloxanes is discharged from the upper part of the continuous flow device, and the polyorganosiloxane with reduced volatile siloxane content is discharged from the discharge part of the continuous flow device. A contained resin slurry can be obtained.

Regardless of whether the batch method or the continuous method is used, the concentration of the resin slurry containing polyonoreganosiloxane used for the treatment is preferably 1% by weight. / ₀ or more, more preferably 5% by weight or more, further 10% by weight or more, preferably 50% by weight or less, more preferably 30% by weight or less, and further preferably 20% by weight or less. If the concentration is too low, productivity and energy efficiency are poor. If the concentration is too high, fusion may occur due to poor stirring in the case of the batch method, and clogging or the like may occur in the case of the continuous method.

The volatile siloxane which is distilled off together with water vapor by the method of the present invention is a concept containing a siloxane compound having a boiling point at atmospheric pressure. For example, a siloxane compound having a boiling point of 350 ° C. or less at atmospheric pressure can be used. Depending on the polyorganosiloxane materials used, examples of volatile siloxanes include hexamethyldisiloxane (MM), octamethyltrisiloxane (MDM), 1,3,5-hexamethylcyclotrisiloxane (D 3), 1, 3, 5, 7— Methylcyclotetrasiloxane (D4), 1,3,5,7,9-decamethylcyclopentapentasiloxane (D5), 1,3,5,7,9,11-dodecamethylcyclohexasiloxane (D6), 1,3 , 5,7,9,11,13-Tetradecamethylcycloheptasiloxane (D7), 1,3,5,7-Octafeninolecyclotetrasiloxane, 1,3,5,7-Tetramethyl-1,1, 3,5,7-tetrafluorocyclotetrasiloxane and the like can be mentioned. Further, a compound in which a methyl group on a silicon atom is partially substituted by a functional group derived from a graft crossing agent such as a mercaptopropyl group, a methacryloyloxypropyl group, a vinyl group, and an aryl group can also be exemplified.

In the present invention, as a method for recovering volatile siloxane distilled out together with water vapor, a gaseous state is passed through a kieselguhr column shown in U.S. Pat. After that, it can be removed and collected as needed. Another preferred method of recovery is to distill the distillate component by cooling it through a commonly known condenser such as heat exchange, and then separate it into a light liquid layer by liquid-liquid separation. Alternatively, a method of recovering using a liquid adsorption filter is more preferable. There are methods of separation and recovery by solid-liquid separation method such as cyclone. According to this method using solid-liquid separation, only volatile siloxane can be easily and efficiently recovered from water and water-soluble components. It is preferable to cool to 17 ° C or less because the melting point of 1,3,5,7-octamethylcyclotetrasiloxane, which is the most abundant component in volatile siloxane, is 17.5 ° C. More preferably, when the temperature is cooled to 10 ° C. or lower, and more preferably 5 ° C. or lower, the recovery by solid-liquid separation can be performed more stably.

Thus, a novel method for producing a polyorganosiloxane-containing resin composition with reduced volatile siloxane and a method for efficiently recovering a volatile siloxane component from a distillate component are provided. Further, the method of the present invention is described in JP-A-07-330905, JP-A-07-278473, JP-A-06-107796 and the like. Using an emulsion obtained by mechanically emulsifying an oily polyorganosiloxane obtained by the method described in JP-A-2001-288269, JP-A-11-222554, US Pat. No. 5,661,215, US Pat. No. 4,600,436, Japanese Patent Application Laid-Open No. 2002-029582, Japanese Patent Application Laid-Open No. 2002-284877, Japanese Patent Application Laid-Open No. 2002-212284, etc. In such a case, a polyorganosiloxane-containing resin having a reduced volatile siloxane content can be obtained, which is preferable.

The present invention also discloses a polyorganosiloxane-containing resin in which volatile siloxane is reduced by heating and stripping the slurry-like polyorganosiloxane-containing resin as described above. According to the method of the present invention, when the polyorganosiloxane-containing resin is composed of a polyorganosiloxane-containing graft copolymer, the heat stripping is performed in a state of emulsion or the like before the graft modification of the polyorganosiloxane particles. After the completion of all chemical reactions such as graft modification, the slurry is converted into a slurry and then heat stripping is performed.Therefore, during the graft polymerization, the graft points derived from the graft modifying agent may have undergone thermal deterioration, etc. Used effectively. For example, when a polyorganosiloxane modified with a mercapto group is used, an undesigned curing reaction such as cross-linking between polyorganosiloxane molecules due to a sulfide bond forming reaction of the mercapto group hardly occurs. In addition, in the method of heating and stripping the emulsion, in order to obtain the polyorganosiloxane-containing resin in a dry state such as a powder, usually, the emulsion of the resin is once heated, cooled, solidified, and then heat-treated again. After the drying process, the method of heating and stripping the slurry of the present invention requires only one heating. This not only suppresses the possibility of unexpected thermal degradation of the resulting resin, it is also advantageous from the viewpoint of energy and productivity, and is maintained in a high-temperature slurry state for a certain period of time. The effect of reducing the water content is also obtained at the same time, and there is an advantage that drying can be completed with less energy and in a shorter time.

The present invention also discloses a flame retardant comprising the polyorganosiloxane-containing resin. For example, the present invention is based on a polyonoleganosiloxane-containing graft copolymer latex. A light polyorganosiloxane-containing resin is obtained, which is used, for example, in polycarbonate or polycarbonate / polyethylene terephthalate resin (PCZPET), polycarbonate polybutylene terephthalate resin (PC / PBT), polycarbonate / acrylonitrile-butadiene-styrene resin (PCZABS). When molded with a polycarbonate-based resin, etc., the graphitic structure is well formed for the above-mentioned reason, so that the resin containing polyoxane-legged siloxane is well dispersed in the polycarbonate-based resin. Good flammability can be provided.

The present invention discloses a resin composition containing the polyorganosiloxane-containing resin and at least one resin selected from thermoplastic resins, thermosetting resins and elastomers. Things. For the same reason as described above, a polyorganosiloxane-containing resin which is favorably dispersed in a matrix resin can be obtained, and good impact resistance and heat shock properties can be imparted, and the brittle temperature can be improved.

The term “elastomer” is a concept including a thermoplastic elastomer.

Specific examples of the thermoplastic resin include polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polymethyl methacrylate (PMMA), Polyarylene, acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-monoacrylate-styrene resin (AAS), butyl chloride (PVC), polystyrene (PSt), methyl methacrylate-styrene copolymer (MS), acrylonitrile Examples include styrene copolymer (AS), nylon, and the like, and mixtures thereof.

Specific examples of the thermosetting resin include an epoxy resin, a phenol resin, a urea resin, a melamine resin, and a polyimide. Specific examples of the elastomer include an acryl rubber such as a butyl acrylate rubber and a butadiene acrylonitrile copolymer. Nitrile rubber such as polymers, chloroprene rubber, natural rubber, butadiene rubber, styrene-butadiene rubber, methyl methacrylate-butyl acrylate block Block copolymer, styrene-1-f-sobutylene block copolymer, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, polyester elastomer, etc., but are not limited thereto. Absent.

In the resin composition of the present invention, a pigment, an antioxidant, an anti-drip agent, a filler, and the like can be added as needed.

By virtue of the novel method for producing a polyonoleganosiloxane-containing resin of the present invention, a polyorganosiloxane-containing resin having a low volatile siloxane content and a reduced environmental load can be provided. Further, a flame retardant having good impact resistance and flame retardancy, or a resin composition having excellent impact resistance, heat shock resistance, embrittlement temperature, and the like can be obtained.

【Example】

The present invention will be specifically described based on examples, but the present invention is not limited thereto. Hereinafter, “parts” means “parts by weight”.

[Solid content]

Dry the latex or slurry in a hot air drier at 130 ° C for 2 hours, and (weight of residue after drying at 130 ° C for 2 hours) / (weight of original latex or slurry before drying) It was calculated as

[Polymerization conversion rate]

(Total charge (parts) X solid content ratio-(Emulsifier charge (parts) + inorganic acid and Z or organic acid charge (parts) + radical polymerization initiator charge (parts) + reducing agent (parts)

+ Redox catalyst (parts))) Calculated as Z (amount of charged monomer (parts)).

[Volume average particle size]

The volume average particle diameters of the seed polymer, polyorganosiloxane particles and graft copolymer were measured in the state of a latex. The volume average particle size (μπι) was measured by a light scattering method using MicRoTRACUUPA150, manufactured by Nikkiso Co., Ltd.

[Toluene insoluble content] The latex was coagulated by adding methanol to the latex and left overnight to remove a transparent liquid layer. Further, methanol was added thereto, and the mixture was allowed to stand overnight. Then, a transparent liquid layer was removed, and then dried to obtain a solid of polyorganosiloxane. This 0.3 g was immersed in 10 Om 1 of toluene at room temperature for 40 hours, and the supernatant was removed to obtain a toluene-insoluble portion in which toluene was swollen, and further dried. The toluene insoluble content was determined as (weight after drying with toluene) z (weight before immersing in toluene).

[Weight average molecular weight (Mw)]

A polyorganosiloxane solid was obtained in the same manner as when obtaining the toluene insoluble content. The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) analysis using the form-mouth soluble matter in this solid. In the GPC analysis, a Waters GPC system was used. The columns were polystyrene gel columns, Shodex K-806 and K805 (manufactured by Showa Denko KK). Analyzed.

[Volatile siloxane content]

It was determined by gas chromatography (GC) analysis. Methyl ethyl ketone was added to latex, resin slurry, or powder for extraction, and octamethinoretrisiloxane was added as an internal standard. Column: Silicone DC—550, 20 wt% Chromosolve WNAW # 60—80, 3 mm × 3 m filled with 80 mm, using a gas chromatograph GC_14B (manufactured by Shimadzu Corporation). The amounts of octamethyltetracyclosiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were determined by analysis, and the ratio of the total weight to the solid resin content was determined by volatile siloxane. The content was determined.

[Moisture content]

The water content of the resin was determined by drying the resin at 130 ° C. for 2 hours and calculating (weight of resin after drying) / (weight of resin before drying).

[Shock resistance]

It was evaluated by an Izod test at 110 ° C. using a notched 18-inch bar according to ASTM D-256. Obscurity]

Evaluated by UL 94 V test. A 120-inch (1.2 mm) thick test specimen was used for the evaluation.

(Production Example 1) Production of seed polymer (SD-1)

400 parts by weight of water and 12 parts by weight of 10% aqueous sodium dodecylbenzenesulfonate (solid content) were placed in a 5-liter flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. After mixing, the temperature was raised to 50 ° C. After the liquid temperature reached 50 ° C, nitrogen substitution was performed. Thereafter, 10 parts by weight of butyl acrylate and 3 parts by weight of t-dodecylmercaptan were added. After 30 minutes, 0.01 part by weight of paramenthane hydroperoxide (solid content), 0.3 part by weight of sodium formaldehyde sulfoxylate (S FS), 0.01 part by weight of disodium ethylenediaminetetraacetate (EDTA) And 0.0025 parts by weight of ferrous sulfate were added and stirred for 1 hour. A mixture of 90 parts by weight of butyl phthalate, 27 parts by weight of t-decyl mercaptan, and 0.09 parts by weight (solid content) of peroxide at the mouth of paramentanide was continuously added over 3 hours. Thereafter, post-polymerization was performed for 2 hours to obtain a latex containing a seed polymer (SD-1) having a particle size of 0.03 / zm and a polymerization conversion of 90% (t-dodecyl mercaptan was regarded as a raw material component). Was.

(Production Examples 2 and 3) Production of polyorganosiloxane particles (S_l, 2)

With the composition shown in Table 1, the mixture was stirred with a homomixer at 7500 rpm for 5 minutes to prepare a siloxane emulsion. Separately, a seed polymer (SD-1) latex corresponding to the solid content in the amount shown in Table 1 was placed in a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet, and thermometer. I charged. The above emulsion was added all at once to the flask. While stirring the system under a nitrogen stream, 1 part by weight (solid content) of a 10% aqueous solution of dodecyl benzene sulfonic acid (DBSA) was added, and then the temperature was raised to 80 ° C. After reaching 80 ° C, react for 15 hours, cool to 25 ° C and leave for 20 hours, then adjust the pH of the system to 6.5 with 3% sodium hydroxide solution to complete the polymerization, and obtain polyorganosiloxane particles ( A latex containing S_l, 2) was obtained. Polymerization conversion rate, poly Table 1 shows the results of measurement of the volume average particle diameter, the toluene insoluble content, the weight average molecular weight (Mw), and the volatile siloxane content of the latex of onoreganosiloxane particles.

【table 1】

SDBS: Dodecyl Penzen Sword Sodium Lefonate

DBSA: Dodecyl penzen sword Lefonic acid

D4: 1,3,5,7-year-old kutamethylcyclotetrasiloxane

DSMA: 3-Metallyloyl xypropyldimethoxymethylsilane

MPrDMS: 3-mercaptopropyldimethoxymethylsilane

(Production Examples 4 and 5) Production of polyorganosiloxane particles (S_3, 4)

1 kg of latex containing polyorganosiloxane particles (S-1, 2) is heated with a heating jacket, a stirrer, a reflux condenser equipped with a container capable of collecting condensed liquid, a steam inlet at the bottom, a pressure gauge A block copolymer of ethylene oxide and propylene oxide with an ethylene oxide content of 22% (made by Nippon Oil & Fats Co., Ltd.) Trade name: Pronone 102) was added in an amount of 0.05 part by weight to 100 parts by weight of the solid content of the latex. 3 k steam supply This was performed at gZ, and after reaching 140 ° C, stripping was started. Stripping was performed for 30 minutes while controlling the amount of distillate gas discharged so that the internal liquid temperature was maintained at 140 to 150 ° C, to obtain a latex containing polyorganosiloxane particles (S-3, 4). Table 1 (parts represent parts by weight) shows the results of measurement of the polymerization conversion, the volume average particle diameter of latex of polyorganosiloxane particles, the toluene insoluble content, the weight average molecular weight (Mw), and the volatile siloxane content. .

(Production Examples 6 and 7) Production of polyorganosiloxane-containing graft copolymer (SG-1, 2)

A 5-lofrasco equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 240 parts by weight of pure water (including the amount brought in from the latex containing polyonoreganosiloxane particles), Then, the latex of polyorganosiloxane particles (S-1, 2) obtained in Production Examples 2 and 3 was charged in the amount shown in Table 2 (however, Table 2 corresponds to the solid content), and the system was stirred under a nitrogen stream. Then, the temperature was raised to the temperature shown in Table 2. One hour after reaching the temperature shown in Table 2, 0.2 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.01 parts by weight of ethylenediamine tetraacetic acid disodium (EDTA), and 0.0025 parts by weight of ferrous sulfate After the addition of the mixture, a mixture of the draft monomers (MG-1) having the composition shown in Table 2 was added all at once, and stirring was continued at the temperature shown in Table 2 for 1 hour. Thereafter, a mixture of the graft monomers (MG-2) having the composition shown in Table 2 was added dropwise over 1 hour, and after the addition was completed, stirring was continued for another 2 hours to obtain the polyorganosiloxane-containing graft copolymer (MG). A latex of SG-1 and 2) was obtained. Table 2 (parts indicate parts by weight) shows the results of measuring the polymerization conversion, the volume average particle diameter of the latex, and the volatile siloxane content of all the graft monomers (total of the first and second stages). [Table 2]

AIMA: aryl methacrylate

MMA: methyl metaperylate

TBPIPC: t-butyl peroxyisopropyl force

CHP: Cumene Hydrate Peroxide

(Production Examples 8, 9) Production of polyorganosiloxane-containing graft copolymer (SG, 1-1, 2)

The same procedure as in Production Examples 6 and 7 was repeated except that a latex containing polyorganosiloxane particles (S-3, 4) was used instead of a latex containing polyorganosiloxane particles (S-1, 2). Copolymer (SG '— 1 2) was obtained. Table 2 shows the results obtained by measuring the polymerization conversion, the volume average particle diameter of the latex, and the volatile siloxane content of all the graft monomers.

(Production examples 10 and 11) Production of polyorganosiloxane-containing graft copolymer (SG'_3, 4)

1 kg of the same latex obtained in Production Examples 6 and 7 was heated with a heating jacket, a stirrer, a reflux condenser equipped with a container capable of collecting condensed liquid, a steam inlet at the bottom, a pressure gauge, and a temperature. Charged into a pressure vessel equipped with a meter, and used as a defoamer as a block copolymer of ethylene oxide and propylene oxide with an ethylene oxide content of 22% (produced by NOF Corporation, trade name: Pronon 102) ) Was added to 0.05 parts by weight to 100 parts by weight of the solid content of the latex. Steam was supplied at 3 kg / hour, and stripping was started after reaching 140 ° C. Stripping was performed for 30 minutes while controlling the amount of distillate gas discharged so that the internal solution temperature was maintained at 140 to 150 ° C, and the polyorganosiloxane-containing graft copolymer (SG, —3, 4) ) Was obtained. Table 2 shows the results.

(Examples 1 and 2) Slurry stripping of polyorganosiloxane-containing graft copolymer (SG-1, 2)

After diluting the latex of the polyorganosiloxane-containing graft copolymer (SG-1, 2) obtained in Production Examples 6 and 7 with water and adjusting the solid content to 15%, 2. A solidified slurry was obtained by adding 4 parts by weight (solid content) of a 5% calcium chloride aqueous solution. This slurry was further diluted with water to have a solid content of 10% by weight. / ₀ was adjusted. This slurry (1 kg) was charged into a pressure vessel equipped with a heating jacket, a stirrer, a reflux condenser equipped with a vessel capable of collecting condensed liquid, a steam inlet at the bottom, a pressure gauge, and a thermometer, and stirred. Steam was supplied at a rate of 3 kg / hour.

After the internal solution temperature reached 145 ° C, stripping was started. The stripping was performed for 30 minutes while controlling the discharge amount of the distillate gas so as to maintain the internal liquid temperature at 140 to 150 ° C, and then the slurry left inside was discharged. Thereafter, the slurry was dewatered to obtain a dewatered cake. During stripping, distilled volatile siloxane is At the same time, the collection vessel was cooled to 5 ° C while condensing and collecting with a reflux condenser. After the stripping was completed, it was confirmed that the liquid temperature in the collection container was 10 ° C or less, and then filtration was performed to collect volatile siloxane. Table 3 shows the volatile siloxane content in the dewatered slurry, the water content of the dewatered cake, and the amount of the recovered volatile siloxane (the ratio to the solid content in the slurry).

Next, the dewatered cake was dried, and 3 parts by weight of the obtained powder was mixed with 0.4 parts of polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., trade name: Polyflon FA-500) in a polycarbonate resin (Idemitsu Petrochemical Co., Ltd.). Made by Co., Ltd., trade name: Toughlon FN1 700A) It was blended to 100 parts by weight. The obtained compound is twin-screw extruder

(TEX44 SS, manufactured by Nippon Steel Corporation) at 270 ° C to produce pellets. The obtained pellets were used to create 18-inch Izod test specimens and 1Z20-inch flame retardancy test specimens using a FAS100 B injection molding machine manufactured by FANUC Co., Ltd., where the cylinder temperature was set to 300 ° C. did. Using the obtained test pieces, evaluation was performed according to the evaluation method described above. Table 3 shows the results.

[Table 3]

Example 1 2 3 4 5 6 Polyorganosiloxane-containing tree SG-1 SG-2 SG-2 SG-2 SG-2 SG-2 Fat

Street pink condition ° c 140- 140 ~ 140 ~ 110 ~ 110 ~ 140 ~

150 150 150 120 120 150 Processing time Time 0.5 0.5 1 0.5 1 0.5 Internal pressure Mpa 0.26 ~ 0.26 ~ 0.26 ~ 0.10 ~ 010 ~ 0.26 ~

0.36 0.36 0.36 0.11 0.11 0.36 Volatile siloxane 5.0% 4.8% 5.1% 9.1% 7.5% 5.2% Content

41% 39% 35% 50% 47% 42% moisture content of dehydrated cake

Recovered siloxane amount 7.7% 6.0% 5.8% 2.6% 3.9% 3.9% Flame retardant Total combustion time 49 44 48 39 42 45

(1/20 inch)

Drip times 0 0 0 0 0 0 Impact resistance-10 ° C kJ / m ² 29 31 28 33 31 29 (Izot strength) (Examples 3 to 5)

Example 2 was the same as Example 2 except that the temperature and processing time of the slurry stripping treatment were as shown in Table 3. Table 3 shows the results.

(Example 6)

During the stripping, the collected container was cooled to 25 ° C while the distilled volatile siloxane was condensed and collected in a reflux condenser with water vapor.After the stripping was completed, the liquid in the collection container was kept at the same temperature. -Same as Example 2 except that the supernatant oil was recovered after standing still. Table 3 shows the results.

(Reference Examples 1 and 2)

After diluting the latex of the polyorganosiloxane-containing graft copolymer (SG-1, 2) obtained in Production Examples 6 and 7 with water and adjusting the solid content to 15%, 2. A coagulated slurry was obtained by adding 4 parts by weight (solid content) of a 5% calcium chloride aqueous solution. The slurry was further diluted with water to adjust the solid content to 10%. The slurry was heated to 95 ° C while being stirred in a stainless steel pot, and heating was continued at 95 ° C for 30 minutes. Thereafter, dehydration was performed to obtain a dehydrated cake. Table 4 shows the volatile siloxane content in the dewatered slurry and the water content of the dewatered cake. The volatile siloxane could not be recovered.

The obtained dehydrated cake was dried, blended with a polycarbonate resin and molded in the same manner as in Example 1, and the same evaluation was performed. Table 4 shows the results.

(Reference Examples 3 and 4)

Instead of the latex of the polyorganosiloxane-containing daraft copolymer (SG-1, 2) obtained in Production Examples 6 and 7, the polyorganosiloxane-containing graft copolymer (SG, 1-1) obtained in Production Examples 8 and 9 was used. , And 2) were the same as in Reference Examples 1 and 2. Table 4 shows the results.

(Reference Examples 5, 6)

Instead of the latex of the polyorganosiloxane-containing graft copolymer (SG-1,2) obtained in Production Examples 6 and 7, the polyorganosiloxane-containing graft copolymer obtained in Production Examples 10 and 11 was used instead. The procedure was the same as in Reference Example 12 except that a grafted copolymer (SG'-34) was used. Table 4 shows the results.

[Table 4]

In the table, SDB S is sodium dodecylbenzenesulfonate, DBSA is dodecylbenzenesulfonic acid, 04 is 135-O-methylcyclotetrasiloxane, DSMA is methacryloyloxypropyl dimethoxymethylsilane, and MPr DMS is mercaptopropyl. Dimethoxymethylsilane, MMA stands for methyl methacrylate, A 1 MA stands for aryl methacrylate, TBP I PC stands for t-butyl peroxyisopropyl carbonate, and CHP stands for cumene hydroxide peroxide.

From the above results, it is understood that the volatile siloxane contained in the dehydrated cake of the polyorganosiloxane-containing resin obtained by the production method of the present invention is reduced. It was also shown that the moisture content of the dehydrated cake was reduced. In other words, this means that the volatile siloxane is volatilized in the subsequent drying step and the drying load is reduced. Further, the method for separating volatile siloxanes from distillate components of the present invention It can be seen that volatile siloxane can be recovered. In addition, the polycarbonate resin containing the polyorganosiloxane-containing resin obtained by the production method of the present invention has the same characteristics as those described above, compared with the resin obtained when stripping is performed in a latex state (Reference Examples 3 to 6). The flame retardancy and strength in some cases were significantly superior, and it was shown to have the same balance of flame retardancy and impact resistance as the resin without stripping (Reference Examples 1 and 2).

Industrial applicability

A novel method for reducing and recovering volatile siloxanes is provided in the production of polyorganosiloxane-containing resins. ADVANTAGE OF THE INVENTION According to the method of this invention, the drying load called thermal energy required at the time of recovering a polyorganosiloxane-containing resin as a powder finally is small, and the environmental load by volatile siloxane in exhaust gas is suppressed. You. At the same time, the resulting polyorganosiloxane-containing resin is resistant to unexpected deterioration in quality due to reduced thermal degradation during manufacturing.For example, when blended with polycarbonate resin, it has good flame retardancy and impact resistance. Sex can be obtained in a well-balanced manner.

Claims

The scope of the claims

1. A method for producing a polyorganosiloxane-containing resin, comprising reducing volatile siloxane by heating and stripping a slurry of the polyorganosiloxane-containing resin.

2. The method for producing a polyorganosiloxane-containing resin according to claim 1, wherein the slurry-like polyorganosiloxane-containing resin is obtained by coagulating a latex-state polyorganosiloxane-containing resin.

3. The polyorganosiloxane-containing resin is a polyorganosiloxane-based graft copolymer obtained by polymerizing one or more monofunctional and / or polyfunctional radical polymerizable monomers in the presence of polyorganosiloxane-based particles. 3. The method for producing the polyorganosiloxane-containing resin according to claim 1 or 2.

The method for producing a polyorganosiloxane-containing resin according to any one of claims 1 to 3, wherein the heat stripping is performed at a temperature of 4.100 ° C or more.

5. The method for producing a polyorganosiloxane xan-containing resin according to any one of claims 1 to 4, wherein steam is supplied to the slurry.

6. The method for producing a polyorganosiloxane-containing resin according to any one of claims 1 to 5, wherein the volatile siloxane is separated by cooling a distillate component containing the volatile siloxane.

7. The method for producing a polyorganosiloxane-containing resin according to claim 6, wherein the volatile siloxane is separated by cooling a distillate component containing the volatile siloxane to 17 ° C. or lower.

8. The method for producing a polyorganosiloxane-containing resin according to claim 7, wherein the volatile siloxane is separated as a solid when the volatile siloxane is separated.

9. A polyorganosiloxane-containing resin having reduced volatile siloxane produced by the method according to any one of claims 1 to 5.

10. A flame retardant comprising the polyorganosiloxane-containing resin according to claim 9.

11. A resin composition comprising the polyorganosiloxane-containing resin according to claim 9 and at least one resin selected from a thermoplastic resin, a thermosetting resin, and an elastomer.